This invention relates to weatherable compositions, and more particularly to weatherable coating compositions for application to thermoplastic substrates.
Various polymeric articles have a problem of long term color instability. This causes yellowing of the polymer, detracting from its transparency and attractiveness. Loss of gloss can also be an undesirable long term phenomenon, as can loss of various physical properties such as impact strength.
Yellowing of polymers is often caused by the action of ultraviolet radiation, which is why such yellowing is frequently designated xe2x80x9cphotoyellowingxe2x80x9d. It is particularly vexing when the polymeric article is to be used outdoors, in direct exposure to sunlight; for example, as a roofing material.
Numerous means for suppressing photoyellowing have been employed and proposed. Many of these involve coating the polymeric substrate with a protective coating comprising a thermoplastic resin, typically an acrylic resin such as poly(methyl methacrylate), in combination with an ultraviolet absorbing compound (UVA) and frequently a solvent, which is removed by evaporation as a final step in the coating operation. Among the commercially available UVA""s of particular interest are hydroxybenzophenones, hydroxyphenylbenzotriazoles, hydroxyphenyltriazines and cyanoacrylates. It is frequently found, however, that these UVA""s do not provide adequate protection against weathering and/or are not compatible with the coating composition at the high loadings required; e.g., about 20-50% by weight based on total solids (resin plus UVA) or 5-10% by weight based on total coating composition including solvent.
Another class of UVA""s, found particularly useful in many environments for protection against weathering in outdoor exposure situations, is the polyaroylresorcinols disclosed in U.S. Pat. No. 5,869,185. They are disclosed therein as constituents of coating materials and/or primers, which may contain resins such as acrylic polymers. As with certain of the previously mentioned UVA""s, however, the presence of polyaroylresorcinols at the levels required in roofing coatings causes incompatibility, as demonstrated by such disadvantageous properties as low solubility, strong tendency to crystallize, and undesirably high viscosity.
Still another class of UVA""s is the silylated diaroylresorcinols. They are described in U.S. Pat. Nos. 5,391,795, 5,679,820 and 5,990,188 as being useful in and compatible with silicone hardcoats and ultraviolet-cured coating compositions comprising acrylic monomers. However, they are relatively expensive to produce and use.
It is of interest, therefore, to develop protective coating compositions containing relatively inexpensive and highly effective UVA""s, said compositions being useful to inhibit photoyellowing and other types of degradation in outdoor use in contact with sunlight.
The present invention is based on the discovery that silylated diaroylresorcinols, in addition to themselves being UVA""s, are effective as compatibilizers for non-silylated polyaroylresorcinols in acrylic coating compositions. Thus, the combination of the two types of resorcinols permits the preparation of highly compatible and weatherable coatings. By xe2x80x9cweatherablexe2x80x9d is meant that ultraviolet degradation as evidenced by photoyellowing is suppressed by use of the coating composition.
One aspect of the invention, therefore, is thermoplastic compositions comprising the following and any reaction products thereof:
at least one thermoplastic acrylic polymer in combination with a minor proportion, effective to improve weatherability, of
(A) at least one substituted resorcinol of the formula 
xe2x80x83and
(B) at least one silylated substituted resorcinol of the formula 
xe2x80x83wherein:
each Z is independently an unsubstituted or substituted aromatic radical,
R1 is hydrogen, a C1-10 alkyl radical or Zxe2x80x94C(O)xe2x80x94,
R2 is a divalent C1-10 aliphatic hydrocarbon radical,
each R3 and R4 is independently a C1-12 alkyl radical, and
n is 0-3;
component B being present in a minor proportion effective to improve solubility and compatibility of component A.
Another aspect of the invention is articles, particularly useful in roofing and other outdoor exposure situations, comprising a thermoplastic substrate and a protective coating thereon, said coating being as described hereinabove.
It is immaterial from the standpoint of the invention, and not entirely certain in any event, whether any chemical reaction takes place between the various components as defined hereinafter. Thus, the invention includes simple physical mixtures of said components and also reaction products thereof.
At least one thermoplastic acrylic polymer is one of the constituents of the compositions of the invention. By xe2x80x9cacrylic polymerxe2x80x9d is meant an addition polymer of at least one monomer derived from acrylic acid or a functional derivative thereof; i.e., an ester, amide, nitrile or the like. Illustrative monomers include acrylic acid, ethyl acrylate, methyl methacrylate, acrylamide and acrylonitrile. The preferred acrylic polymers for many purposes are poly(alkyl acrylates) and poly(alkyl methacrylates), especially poly(methyl methacrylate).
While the use of curable acrylic polymers is within the scope of the invention, it is generally preferred to employ a simple, preformed thermoplastic acrylic polymer which is not capable of further curing. Thus, homo- and copolymers of methyl methacrylate are particularly useful, with the homopolymer, hereinafter sometimes designated xe2x80x9cPMMAxe2x80x9d, being most preferred.
Component A, the substituted resorcinol of formula I, is usually the predominant UVA according to the invention. The Z value therein may be any unsubstituted or substituted aromatic radical, illustrations being phenyl, p-chlorophenyl, p-tolyl, 1-naphthyl and 2-naphthyl; phenyl is generally preferred. R1 is hydrogen (preferably) or alkyl or Zxe2x80x94C(O)xe2x80x94wherein Z is as previously defined. The particularly preferred compound for use as component A is 4,6-dibenzoylresorcinol.
Component B is a silylated substituted resorcinol similar in molecular structure, other than the presence of the silylalkyl group, to component A. The R2 radical may be, for example, ethylene, trimethylene, tetramethylene, pentylene or neopentylene; trimethylene is preferred. The value of n may be from 0 to 3 and is usually 0. Both R3 and R4 may be, for example, methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-methyl-1-propyl, 1-pentyl, 1-octyl, 2-ethylhexyl, 1-decyl or 1-dodecyl, with methyl and ethyl generally being preferred. The most preferred compound of formula II is 2-(3-triethoxysilylpropyl)-4,6-dibenzoylresorcinol.
It is usually preferred to incorporate a solvent in the compositions of the invention. Any solvent effective to dissolve components A and B and the thermoplastic acrylic polymer, and which is non-aggressive to any substrate to which the coating composition is to be applied, may be employed. Suitable solvents may include alcohols, hydroxy ethers, mixtures of the foregoing with water, liquid aliphatic and alicyclic hydrocarbons and chlorofluorocarbons. A frequently preferred solvent is 1-methoxy-2-propanol.
The thermoplastic substrates present in the articles of this invention may be of any suitable thermoplastic material. Examples are polycarbonates, polyesters, polyamides, polyimides and addition polymers including acrylic polymers and polystyrenes (e.g., acrylonitrile-styrene, acrylonitrile-butadiene-styrene and acrylonitrile-styrene-alkyl acrylate copolymers), polyvinyl chloride, polyethylene and polypropylene. Polycarbonates are often preferred, with bisphenol A polycarbonates being most preferred; i.e., polycarbonates derived from 2,2-bis(4-hydroxy-phenyl)propane.
The proportions of components A and B in the compositions of the invention are adjusted for effectiveness to improve weatherability of the coating composition and the underlying substrate, and to improve solubility and compatibility of component A. In general, it is preferred to employ component A as the principal weatherability improving constituent and component B primarily as a compatibilizer, although component B also typically improves weatherability, since the relative cost of component A is substantially lower than that of component B. Moreover, two bases for proportions may be appropriate if the coating composition is prepared and applied in solution.
With this in mind, the proportion of UVA (one or more) based on total solids is most often about 20-50% and preferably about 25-40% by weight. Based on total solution in which it may be prepared, the proportion of UVA is an amount effective to improve weatherability and is typically about 4-12%, preferably about 5-10% and the proportion of acrylic resin about 5-30%, preferably about 10-25%.
As between components A and B, the proportion of component B is an amount effective to improve solubility and compatibility of component A with the acrylic resin and, if present, solvent. This is most often in the range of about 10-50%, preferably about 20-40% of component B by weight of combined UVA""s.
The compositions of this invention may be prepared by simple blending of the constituents thereof; either acrylic resin and UVA""s, or those two in combination with solvent. For preparation of the coated articles of the invention, the coating composition may be applied to the substrate by conventional operations which will depend to some extent on whether a solvent is or is not employed. Thus, such application methods as brushing, spraying, flow coating, dip coating, drawing down and coextrusion may be employed. The thickness of the coating composition on said articles may vary over a wide range, typically in the range of about 1-100 microns.